Formulation of a ware washing solid controlling hardness

ABSTRACT

A water hardness controlling agent includes a polyacrylic acid or salt thereof having a molecular weight of between about 1,000 and about 50,000 g/mol, an acrylic-maleic acid copolymer or salt thereof having a molecular weight of between about 1,000 and about 100,000 g/mol and a phosphonocarboxylic acid or salt thereof. A ratio of acrylic-maleic acid copolymer or salt thereof to polyacrylic acid or salt thereof to phosphonocarboxylic acid or salt thereof in parts per million is about 1-30:10-80:6-20.

CROSS-REFERENCE TO RELATED APPLICATION

The present application is a continuation-in-part application of U.S.patent application Ser. No. 12/730,998, entitled “Novel Formulation of aWare Washing Solid Controlling Hardness,” filed Mar. 24, 2010, which isa continuation-in-part application of U.S. patent application Ser. No.12/510,035, entitled “Novel Formulation of a Ware Washing SolidControlling Hardness”, filed Jul. 27, 2009, which is incorporated hereinby reference.

TECHNICAL FIELD

The present invention relates generally to the field of cleaningcompositions. In particular, the present invention relates to cleaningcompositions for controlling water hardness on surfaces of ware.

BACKGROUND

The level of water hardness, or amount of dissolved solids, in water canhave deleterious effects in many systems. The term “dissolved solids”refers to the presence of calcium and magnesium in water. In general,hard water refers to water having a total dissolved solids (TDS) contentin excess of about 200 ppm. However, hard water often has a TDS contentin excess of about 400 ppm, and even in excess of about 800 ppm. Waterhaving a molar ratio of calcium to magnesium greater than about 1:1 isalso considered to be hard. Often, the molar ratio of calcium tomagnesium in hard water is about 2:1 or about 3:1. Excess calcium in thewater is known to attack other components of the cleaning compositionand to precipitate into solution. Although most locations have hardwater, water hardness tends to vary from one location to another.

When hard water is used in conjunction with cleaning compositions, hardwater can cause precipitation, etching or corrosion of glass, stainingof hard surfaces, or stabilization of bacteria. The hard water can causeprecipitation of anionic surfactants in the cleaning composition beingused, resulting in scaling on the surface being cleaned. For example,when hard water is included as part of the cleaning composition or asthe water of dilution used to clean ware, spotting or filming may remainon the surface after cleaning. Exemplary surfaces that may be affectedinclude, for example: glass, metal and plastic.

SUMMARY

In some aspects, the present invention relates to a water hardnesscontrolling agent including a polyacrylic acid or salt thereof having amolecular weight of between about 1,000 and about 50,000 g/mol, anacrylic-maleic acid copolymer or salt thereof having a molecular weightof between about 1,000 and about 100,000 g/mol and a phosphonocarboxylicacid or salt thereof. A ratio of the acrylic-maleic acid copolymer orsalt thereof to polyacrylic acid or salt thereof to phosphonocarboxylicacid or salt thereof in parts per million is about 1-30:10-80:6-20.

In other aspects, the present invention relates to cleaning compositionsincluding an alkalinity source, a surfactant component and the waterhardness controlling agent described above.

In yet other aspects, the present invention relates to methods ofcleaning a surface. The method includes forming a water hardnesscontrolling agent, adding at least one functional ingredient to thewater hardness controlling agent to form a cleaning composition andapplying the cleaning composition onto a hard surface. The waterhardness controlling agent is formed by mixing an acrylate polymerhaving a molecular weight of between about 1,000 and about 50,000 g/mol,an acrylate-maleic copolymer having a molecular weight of between about1,000 and about 100,000 g/mol and a phosphonocarboxylic acid or saltthereof to form a water hardness controlling agent.

While multiple aspects and embodiments are disclosed, still otheraspects and embodiments of the present invention will become apparent tothose skilled in the art from the following detailed description, whichshows and describes illustrative embodiments of the invention.Accordingly, the drawings and detailed description are to be regarded asillustrative in nature and not restrictive.

DETAILED DESCRIPTION

The present invention relates to hardsurface cleaning compositions andmethods of using the hardsurface cleaning compositions for controllingwater hardness and protecting surfaces. In particular, the hardsurfacecleaning compositions are useful for preventing spotting or filming onthe surface of ware. The cleaning compositions include a water hardnesscontrolling agent including a polyacrylic acid or salts thereof(“polyacrylic acid” or “acrylate polymer”), an acrylic-maleic acidcopolymer or salts thereof (“acrylic-maleic acid copolymer” or“acrylate-maleic copolymer”) and a phosphonocarboxylic acid or saltsthereof (“phosphonocarboxylic acid”). The combination of these threecomponents in specified ratios prevent the formation and deposition ofscale on hard surfaces. Cleaning compositions including this waterhardness controlling agent can be used in various industries, including,but not limited to: warewash (institutional and consumer), laundry, foodand beverage, vehicle care, water care and textile care. In particular,the cleaning compositions can be safely used on glass, plastic and metalsurfaces.

The cleaning compositions generally include a polyacrylic acid, anacrylic-maleic acid copolymer and a phosphonocarboxylic acid forcontrolling water hardness. The polyacrylic acid, acrylic-maleic acidcopolymer and phosphonocarboxylic acid that make up the water hardnesscontrolling agent function to prevent scale formation and depositiononto surfaces being cleaned with the cleaning composition. Withoutwishing to be bound by any particular theory, it is thought that thewater hardness controlling agent performs this function by preventingthe precipitation of calcium carbonate into solution.

The water hardness controlling agent can comprise, consist of, orconsist essentially of a polyacrylic acid, an acrylic-maleic acidcopolymer and a phosphonocarboxylic acid. A water hardness controllingagent consisting essentially of the listed ingredients does not includeadditional ingredients that, if present, would affect the water hardnesscontrolling agent's ability to control water hardness and protectsurfaces.

The cleaning composition can comprise, consist of, or consistessentially of the listed ingredients. A cleaning composition consistingessentially of the listed ingredients does not include additionalingredients that, if present, would affect the composition's ability tocontrol water hardness and protect surfaces.

Examples of suitable polyacrylic acids include, but are not limited to,polyacrylic acids having a molecular weight of between about 1,000 toabout 50,000 g/mol, particularly between about 1,000 and about 35,000g/mol and more particularly between about 1,000 and about 15,000 g/mol.Examples of suitable commercially available polyacrylic acids include,but are not limited to, Acusol 445N and Acusol 445ND available from DowChemical Company, Midland, Mich. and Sokalan PA40, available from BASFCorporation, Florham Park, N.J. Acusol 445N and Acusol 445ND both have amolecular weight of about 4,500 g/mol and Sokalan PA40 has a molecularweight of about 15,000 g/mol. Examples of suitable acrylic-maleic acidcopolymers include, but are not limited to, acrylic-maleic acidcopolymers having a molecular weight of between about 1,000 to about100,000 g/mol, particularly between about 1,000 and about 75,000 g/moland more particularly between about 1,000 and about 50,000 g/mol.Examples of suitable commercially available acrylic-maleic acidcopolymers include, but are not limited to, Acusol 505N and Acusol 448available from Dow Chemical Company, Midland, Mich. and Sokalan CP5,available from BASF Corporation, Florham Park, N.J. Acusol 505N has amolecular weight of about 40,000 g/mol, Acusol 448 has a molecularweight of about 3,500 g/mol and Sokalan CP5 has a molecular weight ofabout 70,000 g/mol. An example of a suitable commercially availablephosphonocarboxylic acid includes, but is not limited to,2-phosphonobutane-1,2,4-tricarboxylic acid. An example of a suitablecommercially available 2-phosphonobutane-1,2,4-tricarboxylic acidincludes, but is not limited to, Bayhibit AM available from MobayChemical Co., Pittsburgh, Pa.

An exemplary formulation parameter of the invention is that the cleaningcomposition includes the polyacrylic acid, the acrylic-maleic acidcopolymer and the phosphonocarboxylic acid at particular ratios. In oneembodiment, the acrylic-maleic acid copolymer, the polyacrylic acid andthe phosphonocarboxylic acid are present in the cleaning composition ata parts per million (ppm) ratio of about 1-30:10-80:6-20 with theacrylic-maleic acid copolymer and the polyacrylic acid being present inthe cleaning composition at about 5 ppm and about 50 ppm, respectively,and particularly at about 15 and about 50 ppm, respectively. Inparticular, the acrylic-maleic acid copolymer, the polyacrylic acid andthe phosphonocarboxylic acid are present in the cleaning composition ata ppm ratio of about 5-30:10-40:6-20. More particularly, theacrylic-maleic acid copolymer, the polyacrylic acid and thephosphonocarboxylic acid are present in the cleaning composition at appm ratio of about 5:40:8.

The cleaning composition also includes an alkalinity source, such as analkali metal hydroxide, alkali metal carbonate, or alkali metalsilicate. Examples of suitable alkalinity sources include, but are notlimited to: sodium hydroxide, potassium hydroxide, sodium carbonate,potassium carbonate or a mixture of alkali metal hydroxide and alkalimetal carbonate. Examples of particularly suitable alkalinity sourcesinclude, but are not limited to: sodium carbonate, sodium hydroxide, ora mixture of sodium carbonate and sodium hydroxide. The alkalinitysource controls the pH of the resulting solution when water is added tothe cleaning composition to form a use solution. The pH of the cleaningcomposition must be maintained in the alkaline range in order to providesufficient detergency properties. In an exemplary embodiment, the pH ofa use solution of the cleaning composition is between approximately 10and approximately 12. If the pH of the cleaning composition is too low,for example, below approximately 10, the cleaning composition may notprovide adequate detergency properties. If the pH of the cleaningcomposition is too high, for example, above approximately 12, thecleaning composition may become caustic and begin to attack the surfaceto be cleaned.

The cleaning compositions also include a surfactant component thatfunctions primarily as a defoamer and as a wetting agent. A variety ofsurfactants may be used, including anionic, nonionic, cationic, andzwitterionic surfactants. For a discussion of surfactants, seeKirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, volume8, pages 900-912, which is incorporated herein by reference.

Examples of suitable anionic surfactants useful in the cleaningcompositions include, but are not limited to: carboxylates such asalkylcarboxylates (carboxylic acid salts) and polyalkoxycarboxylates,alcohol ethoxylate carboxylates, nonylphenol ethoxylate carboxylates andthe like; sulfonates such as alkylsulfonates, alkylbenzenesulfonates,alkylarylsulfonates, sulfonated fatty acid esters and the like; sulfatessuch as sulfated alcohols, sulfated alcohol ethoxylates, sulfatedalkylphenols, alkylsulfates, sulfosuccinates, alkylether sulfates andthe like. Some particularly suitable anionic surfactants include, butare not limited to: sodium alkylarylsulfonate, alpha-olefinsulfonate andfatty alcohol sulfates.

Nonionic surfactants useful in the cleaning compositions include thosehaving a polyalkylene oxide polymer as a portion of the surfactantmolecule. Examples of suitable nonionic surfactants include, but are notlimited to: chlorine-, benzyl-, methyl-, ethyl-, propyl, butyl- andalkyl-capped polyethylene glycol ethers of fatty alcohols; polyalkyleneoxide free nonionics such as alkyl polyglucosides; sorbitan and sucroseesters and their ethoxylates; alkoxylated ethylene diamine; alcoholalkoxylates such as alcohol ethoxylate propoxylates, alcoholpropoxylates, alcohol propoxylate ethoxylate propoxylates, alcoholethoxylate butoxylates and the like; nonylphenol ethoxylate,polyoxyethylene glycol ethers and the like; carboxylic acid esters suchas glycerol esters, polyoxyethylene esters, ethoxylated and glycolesters of fatty acids and the like; carboxylic amides such asdiethanolamine condensates, monoalkanolamine condensates,polyoxyethylene fatty acid amides and the like; and polyalkylene oxideblock copolymers including an ethylene oxide/propylene oxide blockcopolymer. Examples of suitable commercially available nonionicsurfactants include, but are not limited to: PLURONIC, available fromBASF Corporation, Florham Park, N.J. and ABIL B8852, available fromGoldschmidt Chemical Corporation, Hopewell, Va.

Cationic surfactants useful for inclusion in the cleaning compositionsinclude, but are not limited to: amines such as primary, secondary andtertiary amines with C₁₈ alkyl or alkenyl chains, ethoxylatedalkylamines, alkoxylates of ethylenediamine, imidazoles such as a1-(2-hydroxyethyl)-2-imidazoline, a2-alkyl-1-(2-hydroxyethyl)-2-imidazoline and the like; and quaternaryammonium salts, as for example, alkylquaternary ammonium chloridesurfactants such as n-alkyl(C₁₂-C₁₈)dimethylbenzyl ammonium chloride,n-tetradecyldimethylbenzylammonium chloride monohydrate, andnaphthalene-substituted quaternary ammonium chlorides such asdimethyl-1-naphthylmethylammonium chloride. For a more extensive list ofsurfactants, see McCutcheon's Emulsifiers and Detergents, which isincorporated herein by reference.

The cleaning compositions also include water. It should be appreciatedthat the water may be provided as deionized water or as softened waterThe water provided as part of the concentrate can be relatively free ofhardness. It is expected that the water can be deionized to remove aportion of the dissolved solids. Although deionized water is preferredfor formulating the concentrate, the concentrate can be formulated withwater that has not been deionized. That is, the concentrate can beformulated with water that includes dissolved solids, and can beformulated with water that can be characterized as hard water. When thecleaning composition is provided as a liquid, water makes up the balanceof the cleaning composition. When the cleaning composition is providedas a solid, water is provided in an amount such that the amount ofalkalinity source divided by the amount of water plus alkalinity sourceis equal to about 0.6 or greater.

In concentrate form, the cleaning compositions include between about 2.2wt % and about 22 wt % polyacrylic acid, between about 0.1 wt % andabout 20 wt % acrylic-maleic acid copolymer, between about 0.1 wt % andabout 10 wt % phosphonocarboxylic acid, between about 10 wt % and about80 wt % alkalinity source and up to about 3 wt % surfactant component.In particular, the cleaning compositions include between about 2.2 wt %and about 13 wt % polyacrylic acid, between about 0.1 wt % and about11.5 wt % acrylic-maleic acid copolymer, between about 0.5 wt % andabout 5 wt % phosphonocarboxylic acid, between about 20 wt % and about60 wt % alkalinity source and between about 0.5 wt % and about 2 wt %surfactant component. More particularly, the cleaning compositionsinclude between about 2.2 wt % and about 12 wt % polyacrylic acid,between about 0.1 wt % and about 5 wt % acrylic-maleic acid copolymer,between about 0.75 wt % and about 2.25 wt % phosphonocarboxylic acid,between about 30 wt % and about 50 wt % alkalinity source and betweenabout 0.75 wt % and about 1.75 wt % surfactant component. In otherembodiments, similar intermediate concentrations and use concentrationsmay also be present in the cleaning compositions of the invention.

In one embodiment, the cleaning compositions include less thanapproximately 0.55% phosphorous-containing compounds by weight.Particularly, the cleaning composition includes less than approximately0.2% phosphorous-containing compounds by weight. More particularly, thecleaning composition includes less than approximately 0.1%phosphorous-containing compounds by weight.

Additional Functional Materials

The cleaning compositions can include additional components or agents,such as additional functional materials. As such, in some embodiments,the cleaning compositions including the polyacrylic acid, acrylic-maleicacid copolymer, phosphonocarboxylic acid, alkalinity source, surfactantcomponent and water may provide a large amount, or even all of the totalweight of the cleaning composition, for example, in embodiments havingfew or no additional functional materials disposed therein. Thefunctional materials provide desired properties and functionalities tothe cleaning composition. For the purpose of this application, the term“functional materials” include a material that when dispersed ordissolved in a use and/or concentrate solution, such as an aqueoussolution, provides a beneficial property in a particular use. Thecleaning compositions containing the polyacrylic acid, acrylic-maleicacid copolymer, phosphonocarboxylic acid, alkalinity source, surfactantcomponent and water may optionally contain other soil-digestingcomponents, surfactants, disinfectants, sanitizers, acidulants,complexing agents, corrosion inhibitors, foam inhibitors, dyes,thickening or gelling agents, and perfumes. Some particular examples offunctional materials are discussed in more detail below, but it shouldbe understood by those of skill in the art and others that theparticular materials discussed are given by way of example only, andthat a broad variety of other functional materials may be used.

Thickening Agents

Thickeners useful in the present invention include those compatible withalkaline systems. The viscosity of the cleaning compositions increaseswith the amount of thickening agent, and viscous compositions are usefulfor uses where the cleaning composition clings to the surface. Suitablethickeners can include those which do not leave contaminating residue onthe surface to be treated. Generally, thickeners which may be used inthe present invention include natural gums such as xanthan gum, guargum, modified guar, or other gums from plant mucilage; polysaccharidebased thickeners, such as alginates, starches, and cellulosic polymers(e.g., carboxymethyl cellulose, hydroxyethyl cellulose, and the like);polyacrylates thickeners; and hydrocolloid thickeners, such as pectin.Generally, the concentration of thickener employed in the presentcompositions or methods will be dictated by the desired viscosity withinthe final composition. However, as a general guideline, the viscosity ofthickener within the present composition ranges from about 0.1 wt % toabout 3 wt %, from about 0.1 wt % to about 2 wt %, or about 0.1 wt % toabout 0.5 wt %.

Dyes and Fragrances

Various dyes, odorants including perfumes, and other aesthetic enhancingagents may also be included in the cleaning compositions. Dyes may beincluded to alter the appearance of the composition, as for example, anyof a variety of FD&C dyes, D&C dyes, and the like. Additional suitabledyes include Direct Blue 86 (Miles), Fastusol Blue (Mobay ChemicalCorp.), Acid Orange 7 (American Cyanamid), Basic Violet 10 (Sandoz),Acid Yellow 23 (GAF), Acid Yellow 17 (Sigma Chemical), Sap Green(Keyston Analine and Chemical), Metanil Yellow (Keystone Analine andChemical), Acid Blue 9 (Hilton Davis), Sandolan Blue/Acid Blue 182(Sandoz), Hisol Fast Red (Capitol Color and Chemical), Fluorescein(Capitol Color and Chemical), Acid Green 25 (Ciba-Geigy), Pylakor AcidBright Red (Pylam), and the like. Fragrances or perfumes that may beincluded in the compositions include, for example, terpenoids such ascitronellol, aldehydes such as amyl cinnamaldehyde, a jasmine such asC1S-jasmine or jasmal, vanillin, and the like.

Rinse Aids

The cleaning compositions can optionally include a rinse aidcomposition, for example a rinse aid formulation containing a wetting orsheeting agent combined with other optional ingredients in a solidcomposition made using the binding agent. The rinse aid components arecapable of reducing the surface tension of the rinse water to promotesheeting action and/or to prevent spotting or streaking caused by beadedwater after rinsing is complete, for example in warewashing processes.Examples of sheeting agents include, but are not limited to: polyethercompounds prepared from ethylene oxide, propylene oxide, or a mixture ina homopolymer or block or heteric copolymer structure. Such polyethercompounds are known as polyalkylene oxide polymers, polyoxyalkylenepolymers or polyalkylene glycol polymers. Such sheeting agents require aregion of relative hydrophobicity and a region of relativehydrophilicity to provide surfactant properties to the molecule.

Bleaching Agents

The cleaning compositions can optionally include a bleaching agent forlightening or whitening a substrate, and can include bleaching compoundscapable of liberating an active halogen species, such as Cl₂, Br₂, —OCl—and/or —OBr—, or the like, under conditions typically encountered duringthe cleansing process. Examples of suitable bleaching agents include,but are not limited to: chlorine-containing compounds such as chlorine,a hypochlorite or chloramines. Examples of suitable halogen-releasingcompounds include, but are not limited to: alkali metaldichloroisocyanurates, alkali metal hypochlorites, monochloramine, anddichloroamine. Encapsulated chlorine sources may also be used to enhancethe stability of the chlorine source in the composition (see, forexample, U.S. Pat. Nos. 4,618,914 and 4,830,773, the disclosures ofwhich are incorporated by reference herein). The bleaching agent mayalso include an agent containing or acting as a source of active oxygen.The active oxygen compound acts to provide a source of active oxygen andmay release active oxygen in aqueous solutions. An active oxygencompound can be inorganic, organic or a mixture thereof. Examples ofsuitable active oxygen compounds include, but are not limited to:peroxygen compounds, peroxygen compound adducts, hydrogen peroxide,perborates, sodium carbonate peroxyhydrate, phosphate peroxyhydrates,potassium permonosulfate, and sodium perborate mono and tetrahydrate,with and without activators such as tetraacetylethylene diamine.

Sanitizers/Anti-Microbial Agents

The cleaning compositions can optionally include a sanitizing agent (orantimicrobial agent). Sanitizing agents, also known as antimicrobialagents, are chemical compositions that can be used to prevent microbialcontamination and deterioration of material systems, surfaces, etc.Generally, these materials fall in specific classes including phenolics,halogen compounds, quaternary ammonium compounds, metal derivatives,amines, alkanol amines, nitro derivatives, anilides, organosulfur andsulfur-nitrogen compounds and miscellaneous compounds.

The given antimicrobial agent, depending on chemical composition andconcentration, may simply limit further proliferation of numbers of themicrobe or may destroy all or a portion of the microbial population. Theterms “microbes” and “microorganisms” typically refer primarily tobacteria, virus, yeast, spores, and fungus microorganisms. In use, theantimicrobial agents are typically formed into a solid functionalmaterial that when diluted and dispensed, optionally, for example, usingan aqueous stream forms an aqueous disinfectant or sanitizer compositionthat can be contacted with a variety of surfaces resulting in preventionof growth or the killing of a portion of the microbial population. Athree log reduction of the microbial population results in a sanitizercomposition. The antimicrobial agent can be encapsulated, for example,to improve its stability.

Examples of suitable antimicrobial agents include, but are not limitedto, phenolic antimicrobials such as pentachlorophenol;orthophenylphenol; chloro-p-benzylphenols; p-chloro-m-xylenol;quaternary ammonium compounds such as alkyl dimethylbenzyl ammoniumchloride; alkyl dimethylethylbenzyl ammonium chloride; octyldecyldimethyl ammonium chloride; dioctyl dimethyl ammonium chloride; anddidecyl dimethyl ammonium chloride. Examples of suitable halogencontaining antibacterial agents include, but are not limited to: sodiumtrichloroisocyanurate, sodium dichloro isocyanate (anhydrous ordihydrate), iodine-poly(vinylpyrrolidinone) complexes, bromine compoundssuch as 2-bromo-2-nitropropane-1,3-diol, and quaternary antimicrobialagents such as benzalkonium chloride, didecyldimethyl ammonium chloride,choline diiodochloride, and tetramethyl phosphonium tribromide. Otherantimicrobial compositions such ashexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine, dithiocarbamates suchas sodium dimethyldithiocarbamate, and a variety of other materials areknown in the art for their antimicrobial properties.

It should also be understood that active oxygen compounds, such as thosediscussed above in the bleaching agents section, may also act asantimicrobial agents, and can even provide sanitizing activity. In fact,in some embodiments, the ability of the active oxygen compound to act asan antimicrobial agent reduces the need for additional antimicrobialagents within the composition. For example, percarbonate compositionshave been demonstrated to provide excellent antimicrobial action.

Complexing Agents

In some embodiments, the cleaning compositions can optionally include acomplexing agent. The complexing agent can include an organic complexingagent, an inorganic complexing agent, and mixtures thereof. Inorganiccomplexing agents include, but are not limited to, such compounds assodium pyrophosphate, and sodium tripolyphosphate. Organic complexingagents include, but are not limited to, both polymeric and smallmolecule complexing agents. Polymeric complexing agents can includeionomer compositions such as polyacrylic acids compounds. Small moleculeorganic complexing agents include amino-carboxylates, including but notlimited to, salts of ethylenediaminetetracetic acid (EDTA) andhydroxyethylenediaminetetracetic acid, nitrilotriacetic acid,ethylenediaminetetrapropionates, triethylenetetraminehexacetates,glutamic acid-N,N-diacetic acid tetrasodium salt, andmethylglycinediacetic acid trisodium salt. The aminocarboxylates can beused in either the acid or the salt forms, for example, alkali metalammonium and substituted ammonium salts. Examples of suitablecommercially available aminocarboxylates include, but are not limitedto, Dissolvine® GL, commercially available from Akzo Nobel, and TrilonM®, commercially available from BASF. Phosphonates are also suitable foruse as complexing agents in the compositions of the invention andinclude, but are not limited to ethylenediaminetetra(methylenephosphonate), nitrilotrismethylenephosphonate,diethylenetriaminepenta(methylene phosphonate), hydroxyethylidenediphosphonate, and combinations thereof.

In some embodiments, the cleaning compositions include a complexingagent at between about 0.001 wt % and about 80 wt %, between about 0.1wt % and about 50 wt %, or between about 1.0 wt % and about 30 wt %.

Activators

In some embodiments, the antimicrobial activity or bleaching activity ofthe cleaning compositions can be enhanced by the addition of a materialwhich, when the cleaning composition is placed in use, reacts with theactive oxygen to form an activated component. For example, in someembodiments, a peracid or a peracid salt is formed. For example, in someembodiments, tetraacetylethylene diamine can be included within thedetergent composition to react with the active oxygen and form a peracidor a peracid salt that acts as an antimicrobial agent. Other examples ofactive oxygen activators include transition metals and their compounds,compounds that contain a carboxylic, nitrile, or ester moiety, or othersuch compounds known in the art. In an embodiment, the activatorincludes tetraacetylethylene diamine; transition metal; compound thatincludes carboxylic, nitrile, amine, or ester moiety; or mixturesthereof. In some embodiments, an activator for an active oxygen compoundcombines with the active oxygen to form an antimicrobial agent.

In some embodiments, the cleaning compositions are in the form of asolid block, and an activator material for the active oxygen is coupledto the solid block. The activator can be coupled to the solid block byany of a variety of methods for coupling one solid detergent compositionto another. For example, the activator can be in the form of a solidthat is bound, affixed, glued or otherwise adhered to the solid block.Alternatively, the solid activator can be formed around and encasing theblock. By way of further example, the solid activator can be coupled tothe solid block by the container or package for the detergentcomposition, such as by a plastic or shrink wrap or film.

Builders or Fillers

The cleaning compositions can optionally include a minor but effectiveamount of one or more of a filler which does not necessarily perform asa cleaning agent per se, but may cooperate with a cleaning agent toenhance the overall cleaning capacity of the composition. Examples ofsuitable fillers include, but are not limited to: sodium sulfate, sodiumchloride, starch, sugars, and C1-C10 alkylene glycols such as propyleneglycol.

pH Buffering Agents

Additionally, the cleaning compositions can be formulated such thatduring use in aqueous operations, for example in aqueous cleaningoperations, the wash water will have a desired pH. For example, asouring agent may be added to the cleaning composition such that the pHof the textile approximately matches the proper processing pH. Thesouring agent is a mild acid used to neutralize residual alkalines andreduce the pH of the textile such that when the garments come intocontact with human skin, the textile does not irritate the skin.Examples of suitable souring agents include, but are not limited to:phosphoric acid, formic acid, acetic acid, hydrofluorosilicic acid,saturated fatty acids, dicarboxylic acids, tricarboxylic acids, and anycombination thereof. Examples of saturated fatty acids include, but arenot limited to: those having 10 or more carbon atoms such as palmiticacid, stearic acid, and arachidic acid (C20). Examples of dicarboxylicacids include, but are not limited to: oxalic acid, tartaric acid,glutaric acid, succinic acid, adipic acid, and sulfamic acid. Examplesof tricarboxylic acids include, but are not limited to: citric acid andtricarballylic acids. Examples of suitable commercially availablesouring agents include, but are not limited to: TurboLizer, InjectionSour, TurboPlex, AdvaCare 120 Sour, AdvaCare 120 Sanitizing Sour,CarboBrite, and Econo Sour, all available from Ecolab Inc., St. Paul,Minn.

Fabric Relaxants

A fabric relaxant may be added to the cleaning compositions to increasethe smoothness appearance of the surface of the textile.

Fabric Softeners

A fabric softener may also be added to the cleaning compositions tosoften the feel of the surface of the textile. An example of a suitablecommercially available fabric softener includes, but is not limited to,TurboFresh, available from Ecolab Inc., St. Paul, Minn.

Soil Releasing Agents

The cleaning compositions can include soil releasing agents that can beprovided for coating the fibers of textiles to reduce the tendency ofsoils to attach to the fibers. Examples of suitable commerciallyavailable soil releasing agents include, but are not limited to:polymers such as Repel-O-Tex SRP6 and Repel-O-Tex PF594, available fromRhodia, Cranbury, N.J.; TexaCare 100 and TexaCare 240, available fromClariant Corporation, Charlotte, N.C.; and Sokalan HP22, available fromBASF Corporation, Florham Park, N.J.

Defoaming Agents

The cleaning compositions can optionally include a minor but effectiveamount of a defoaming agent for reducing the stability of foam. Examplesof suitable defoaming agents include, but are not limited to: siliconecompounds such as silica dispersed in polydimethylsiloxane, fattyamides, hydrocarbon waxes, fatty acids, fatty esters, fatty alcohols,fatty acid soaps, ethoxylates, mineral oils, polyethylene glycol esters,and alkyl phosphate esters such as monostearyl phosphate. A discussionof defoaming agents may be found, for example, in U.S. Pat. No.3,048,548 to Martin et al., U.S. Pat. No 3,334,147 to Brunelle et al.,and U.S. Pat. No 3,442,242 to Rue et al., the disclosures of which areincorporated by reference herein.

Anti-Redeposition Agents

The cleaning compositions can optionally include an anti-redepositionagent capable of facilitating sustained suspension of soils in acleaning solution and preventing the removed soils from beingredeposited onto the substrate being cleaned. Examples of suitableanti-redeposition agents include, but are not limited to: fatty acidamides, fluorocarbon surfactants, complex phosphate esters,polyacrylates, styrene maleic anhydride copolymers, and cellulosicderivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose.

Stabilizing Agents

The cleaning compositions may also include stabilizing agents. Examplesof suitable stabilizing agents include, but are not limited to: borate,calcium/magnesium ions, propylene glycol, and mixtures thereof.

Dispersants

The cleaning compositions may also include dispersants. Examples ofsuitable dispersants that can be used in the solid detergent compositioninclude, but are not limited to: maleic acid/olefin copolymers,polyacrylic acid, and mixtures thereof.

Optical Brighteners

The cleaning compositions can optionally include an optical brightener,also referred to as a fluorescent whitening agent or a fluorescentbrightening agent, and can provide optical compensation for the yellowcast in fabric substrates.

Fluorescent compounds belonging to the optical brightener family aretypically aromatic or aromatic heterocyclic materials often containing acondensed ring system. A feature of these compounds is the presence ofan uninterrupted chain of conjugated double bonds associated with anaromatic ring. The number of such conjugated double bonds is dependenton substituents as well as the planarity of the fluorescent part of themolecule. Most brightener compounds are derivatives of stilbene or4,4′-diamino stilbene, biphenyl, five membered heterocycles (triazoles,oxazoles, imidazoles, etc.) or six membered heterocycles(naphthalamides, triazines, etc.). The choice of optical brighteners foruse in compositions will depend upon a number of factors, such as thetype of composition, the nature of other components present in thecomposition, the temperature of the wash water, the degree of agitation,and the ratio of the material washed to the tub size. The brightenerselection is also dependent upon the type of material to be cleaned,e.g., cottons, synthetics, etc. Because most laundry detergent productsare used to clean a variety of fabrics, the detergent compositions maycontain a mixture of brighteners which are effective for a variety offabrics. It is of course necessary that the individual components ofsuch a brightener mixture be compatible.

Examples of suitable optical brighteners are commercially available andwill be appreciated by those skilled in the art. At least somecommercial optical brighteners can be classified into subgroups,including, but are not limited to: derivatives of stilbene, pyrazoline,carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles,5- and 6-membered-ring heterocycles, and other miscellaneous agents.Examples of particularly suitable optical brightening agents include,but are not limited to: distyryl biphenyl disulfonic acid sodium salt,and cyanuric chloride/diaminostilbene disulfonic acid sodium salt.Examples of suitable commercially available optical brightening agentsinclude, but are not limited to: Tinopal 5 BM-GX, Tinopal CBS-CL,Tinopal CBS-X, and Tinopal AMS-GX, available from Ciba SpecialtyChemicals Corporation, Greensboro, N.C. Examples of optical brightenersare also disclosed in “The Production and Application of FluorescentBrightening Agents”, M. Zahradnik, Published by John Wiley & Sons, NewYork (1982), the disclosure of which is incorporated herein byreference.

Suitable stilbene derivatives include, but are not limited to:derivatives of bis(triazinyl)amino-stilbene, bisacylamino derivatives ofstilbene, triazole derivatives of stilbene, oxadiazole derivatives ofstilbene, oxazole derivatives of stilbene, and styryl derivatives ofstilbene.

Anti-Static Agents

The cleaning compositions can include an anti-static agent such as thosecommonly used in the laundry drying industry to provide anti-staticproperties. Anti-static agents can generate a percent static reductionof at least about 50% when compared with a textile that is not subjectedto treatment. The percent static reduction can be greater than 70% andit can be greater than 80%. An example of an anti-static agent includes,but is not limited to, an agent containing quaternary groups.

Anti-Wrinkling Agents

The cleaning compositions can include anti-wrinkling agents to provideanti-wrinkling properties. Examples of anti-wrinkling suitable agentsinclude, but are not limited to: siloxane or silicone containingcompounds and quaternary ammonium compounds. Particularly suitableexamples of anti-wrinkling agents include, but are not limited to:polydimethylsiloxane diquaternary ammonium, silicone copolyol fattyquaternary ammonium, and polydimethyl siloxane with polyoxyalkylenes.Examples of commercially available anti-wrinkling agents include, butare not limited to: Rewoquat SQ24, available from Degussa/GoldschmidtChemical Corporation, Hopewell, Va.; Lube SCI-Q, available from LambertTechnologies; and Tinotex CMA, available from Ciba Specialty ChemicalsCorporation, Greensboro, N.C.

Odor-Capturing Agents

The cleaning compositions can include odor capturing agents. In general,odor capturing agents are believed to function by capturing or enclosingcertain molecules that provide an odor. Examples of suitable odorcapturing agents include, but are not limited to: cyclodextrins and zincricinoleate.

Fiber Protection Agents

The cleaning compositions can include fiber protection agents that coatthe fibers of the textile to reduce or prevent disintegration and/ordegradation of the fibers. An example of a fiber protection agentincludes, but is not limited to, cellulosic polymers.

Color Protection Agents

The cleaning compositions can include color protection agents forcoating the fibers of a textile to reduce the tendency of dyes to escapethe textile into water. Examples of suitable color protection agentsinclude, but are not limited to: quaternary ammonium compounds andsurfactants. Examples of particularly suitable color protection agentsinclude, but are not limited to: di-(nortallow carboxyethyl)hydroxyethylmethyl ammonium methylsulfate and cationic polymers. Examples ofcommercially available surfactant color protection agents include, butare not limited to: Varisoft WE 21 CP and Varisoft CCS-1, available fromDegussa/Goldschmidt Chemical Corporation, Hopewell, Va.; Tinofix CL fromCiba Specialty Chemicals Corporation, Greensboro, N.C.; Color CareAdditive DFC 9, Thiotan TR, Nylofixan P-Liquid, Polymer VRN, CartaretinF-4, and Cartaretin F-23, available from Clariant Corporation,Charlotte, N.C.; EXP 3973 Polymer, available from Alcoa Inc.,Pittsburgh, Pa.; and Coltide, available from Croda International Plc,Edison N.J.

UV Protection Agents

The cleaning compositions can include a UV protection agent to providethe fabric with enhanced UV protection. In the case of clothing, it isbelieved that by applying UV protection agents to the clothing, it ispossible to reduce the harmful effects of ultraviolet radiation on skinprovided underneath the clothing. As clothing becomes lighter in weight,UV light has a greater tendency to penetrate the clothing and the skinunderneath the clothing may become sunburned. An example of a suitablecommercially available UV protection agent includes, but is not limitedto, Tinosorb FD, available from Ciba Specialty Chemicals Corporation,Greensboro, N.C.

Anti-Pilling Agents

The cleaning compositions can include an anti-pilling agent that acts onportions of fibers that stick out or away from the fiber. Anti-pillingagents can be available as enzymes such as cellulase enzymes. Examplesof commercially available anti-pilling agents include, but are notlimited to: Puradex, available from Genencor International, Pal Alto,Calif.; and Endolase and Carezyme, available from Novozyme, Franklinton,N.C.

Water Repellency Agents

The cleaning compositions can include water repellency agents that canbe applied to textile to enhance water repellent properties. Examples ofstuiable water repellenancy agents include, but are not limited to:perfluoroacrylate copolymers, hydrocarbon waxes, and polysiloxanes.

Hardening Agents/Solubility Modifiers

The cleaning compositions may include a minor but effective amount of ahardening agent. Examples of suitable hardening agents include, but arenot limited to: an amide such stearic monoethanolamide or lauricdiethanolamide, an alkylamide, a solid polyethylene glycol, a solidEO/PO block copolymer, starches that have been made water-solublethrough an acid or alkaline treatment process, and various inorganicsthat impart solidifying properties to a heated composition upon cooling.Such compounds may also vary the solubility of the composition in anaqueous medium during use such that the cleaning agent and/or otheractive ingredients may be dispensed from the solid composition over anextended period of time.

Adjuvants

The cleaning compositions can also include any number of adjuvants.Specifically, the cleaning composition can include stabilizing agents,wetting agents, foaming agents, corrosion inhibitors, biocides orhydrogen peroxide among any number of other constituents which can beadded to the composition. Such adjuvants can be pre-formulated with thepresent composition or added to the system simultaneously, or evenafter, the addition of the present composition. The cleaning compositioncan also contain any number of other constituents as necessitated by theapplication, which are known and which can facilitate the activity ofthe present compositions.

Embodiments of the Present Compositions

Exemplary concentrate compositions of the cleaning compositions areprovided in the following table.

TABLE 1 Exemplary Compositions Range Range Range Component (Wt %) (Wt %)(Wt %) Polyacrylate Polymer (45%) 2.2-22.2 2.2-13   2.22-12  Acrylate-Maleic Copolymer 0.1-20   0.1-11.5 0.1-5   Phosphonocarboxylicacid 0.1-10   0.5-5   0.75-2.25 Sodium Hydroxide, liquid (50%) 0-60 1-40 2-20 Sodium Hydroxide, beads 0-99 2-75 10-60 Water Balance BalanceBalance Ethylene Oxide-Propylene Oxide 0-3  0.5-2   0.75-1.75 blockcopolymer Sodium Sulfate, anhydrous 0-50 2-30  5-20 Sodium Carbonate0-99 5-75 10-45 Complexing Agent 0.1-50   1-40 10-30

The concentrate compositions of the present invention can be provided asa solid, powder, liquid, or gel, or a combination thereof. In oneembodiment, the cleaning compositions may be provided as a concentratesuch that the cleaning composition is substantially free of any addedwater or the concentrate may contain a nominal amount of water. Theconcentrate can be formulated without any water or can be provided witha relatively small amount of water in order to reduce the expense oftransporting the concentrate. For example, the composition concentratecan be provided as a capsule or pellet of compressed powder, a solid, orloose powder, either contained by a water soluble material or not. Inthe case of providing the capsule or pellet of the composition in amaterial, the capsule or pellet can be introduced into a volume ofwater, and if present the water soluble material can solubilize,degrade, or disperse to allow contact of the composition concentratewith the water. For the purposes of this disclosure, the terms “capsule”and “pellet” are used for exemplary purposes and are not intended tolimit the delivery mode of the invention to a particular shape.

When provided as a liquid concentrate composition, the concentrate canbe diluted through dispensing equipment using aspirators, peristalticpumps, gear pumps, mass flow meters, and the like. This liquidconcentrate embodiment can also be delivered in bottles, jars, dosingbottles, bottles with dosing caps, and the like. The liquid concentratecomposition can be filled into a multi-chambered cartridge insert thatis then placed in a spray bottle or other delivery device filled with apre-measured amount of water.

In yet another embodiment, the concentrate composition can be providedin a solid form that resists crumbling or other degradation until placedinto a container. Such container may either be filled with water beforeplacing the composition concentrate into the container, or it may befilled with water after the composition concentrate is placed into thecontainer. In either case, the solid concentrate composition dissolves,solubilizes, or otherwise disintegrates upon contact with water. In aparticular embodiment, the solid concentrate composition dissolvesrapidly thereby allowing the concentrate composition to become a usecomposition and further allowing the end user to apply the usecomposition to a surface in need of cleaning.

In another embodiment, the solid concentrate composition can be dilutedthrough dispensing equipment whereby water is sprayed at the solid blockforming the use solution. The water flow is delivered at a relativelyconstant rate using mechanical, electrical, or hydraulic controls andthe like. The solid concentrate composition can also be diluted throughdispensing equipment whereby water flows around the solid block,creating a use solution as the solid concentrate dissolves. The solidconcentrate composition can also be diluted through pellet, tablet,powder and paste dispensers, and the like.

The water used to dilute the concentrate (water of dilution) can beavailable at the locale or site of dilution. The water of dilution maycontain varying levels of hardness depending upon the locale. Servicewater available from various municipalities have varying levels ofhardness. It is desirable to provide a concentrate that can handle thehardness levels found in the service water of various municipalities.The water of dilution that is used to dilute the concentrate can becharacterized as hard water when it includes at least 1 grain hardness.It is expected that the water of dilution can include at least 5 grainshardness, at least 10 grains hardness, or at least 20 grains hardness.

It is expected that the concentrate will be diluted with the water ofdilution in order to provide a use solution having a desired level ofdetersive properties. If the use solution is required to remove tough orheavy soils, it is expected that the concentrate can be diluted with thewater of dilution at a weight ratio of at least 1:1 and up to 1:8. If alight duty cleaning use solution is desired, it is expected that theconcentrate can be diluted at a weight ratio of concentrate to water ofdilution of up to about 1:2000.

In an alternate embodiment, the cleaning compositions may be provided asa ready-to-use (RTU) composition. If the cleaning composition isprovided as a RTU composition, a more significant amount of water isadded to the cleaning composition as a diluent. When the concentrate isprovided as a liquid, it may be desirable to provide it in a flowableform so that it can be pumped or aspirated. It has been found that it isgenerally difficult to accurately pump a small amount of a liquid. It isgenerally more effective to pump a larger amount of a liquid.Accordingly, although it is desirable to provide the concentrate with aslittle water as possible in order to reduce transportation costs, it isalso desirable to provide a concentrate that can be dispensedaccurately. In the case of a liquid concentrate, it is expected thatwater will be present in an amount of up to about 90 wt %, particularlybetween about 20 wt % and about 85 wt %, more particularly between about30 wt % and about 80 wt. % and most particularly between about 50 wt %and about 80 wt %.

Compositions of the invention may be useful to clean a variety ofsurfaces. Invention compositions may be used to clean soils on hardsurfaces including but not limited to ceramics, ceramic tile, grout,granite, concrete, mirrors, enameled surfaces, metals includingaluminum, brass, stainless steel and the like. Compositions of theinvention may also be used to clean soiled linens such as towels,sheets, and nonwoven webs. As such, compositions of the invention areuseful to formulate hard surface cleaners, laundry detergents, ovencleaners, hand soaps, automotive detergents, and warewashing detergentswhether automatic or manual.

EXAMPLES

The present invention is more particularly described in the followingexamples that are intended as illustrations only, since numerousmodifications and variations within the scope of the present inventionwill be apparent to those skilled in the art. Unless otherwise noted,all parts, percentages, and ratios reported in the following examplesare on a weight basis, and all reagents used in the examples wereobtained, or are available, from the chemical suppliers described below,or may be synthesized by conventional techniques.

Materials Used

Acusol 445N (45%): an acrylate polymer having a molecular weight ofabout 4,500 g/mol, available from Dow Chemical Company, Midland, Mich.

Acusol 445ND: a solid acrylate polymer having a molecular weight ofabout 4,500 g/mol, available from Dow Chemical Company, Midland, Mich.

Sokalan PA40 (35%): an acrylate polymer having a molecular weight ofabout 15,000 g/mol, available from BASF Corporation, Florham Park, N.J.

Acusol 448 (46%): an acrylate-maleic copolymer having a molecular weightof about 3,500 g/mol, available from Dow Chemical Company, Midland,Mich.

Acusol 505N (35%): an acrylate-maleic copolymer having a molecularweight of about 40,000 g/mol, available from Dow Chemical Company,Midland, Mich.

Sokalan CP5 (45%): an acrylate-maleic copolymer having a molecularweight of about 70,000 g/mol, available from BASF Corporation, FlorhamPark, N.J.

Bayhibit AM (50%): a 2-phosphonobutane-1,2,4-tricarboxylic acid,available from Mobay Chemical Co., Pittsburgh, Pa.

Pluronic N3: an ethylene oxide/propylene oxide block copolymer,available from BASF Corporation, Florham Park, N.J.

Beaker Test

As an initial test to determine the ability of solutions to controlwater hardness, a hardness solution and a sodium bicarbonate solutionwere first prepared. The hardness solution was prepared by dissolvingabout 33.45 grams of CaCl₂.2H₂O+23.24 grams of MgCl₂.6H₂O in a 1 litervolumetric flask and diluting to volume with deionized water. The sodiumbicarbonate solution was prepared by dissolving about 56.25 grams ofNaHCO₃.2H₂O in a 1 liter volumetric flask and diluting to volume withdeionized water.

After the solutions were prepared, about 1000 (milliliters) of deionizedwater and a 1.5 inch stir bar was added to each of four beakers. Thebeakers were placed on stirrers and heated. About 5.0 mls of sodiumbicarbonate solution was then added to each beaker. When the temperatureof the solutions in the beakers reached about 85° F., a pre-determinedvolume (1 ml =2 grains) of hardness solution was added to each of thebeakers. The hardness solution was added in increments of 2 grainsunless otherwise specified.

A pre-determined amount of test solution was added to each beaker,equaling about 1000 ppm. After the solutions in the beakers werecompletely mixed, the stirrer was turned to low speed.

When the temperature of the solutions again reached about 85° F., aninitial transmittance reading was taken (0 minutes). Transmittancereadings were then taken at 560 nm, at 85° F., 140° F. and 160° F.Generally, the higher the transmittance reading, the more clear thesolution, indicating that calcium carbonate did not precipitate intosolution.

Samples 1, 2, 3, 4, 5, 6 and 7

Samples 1, 2, 3, 4, 5, 6 and 7 included varying concentrations of anacrylate-maleic copolymer having a molecular weight of about 40,000g/mol. In particular, the samples were prepared by first mixing about97.14 grams of deionized water and about 2.86 grams of Acusol 505N andthen making the appropriate dilution.

Table 2 shows the concentration and transmittance readings at 85° F.,140° F. and 160° F. of each of Samples 1-7. The appearance of each ofthe solutions was also noted.

TABLE 2 Concen- tration Transmittance Reading (%) Sample (ppm) 85° F.140° F. 160° F. 1 2.5 97.0; clear 76.6; cloudy 69.5; cloudy 2 5 94.6; v.slight haze 83.1; v. hazy 82.9; v. hazy 3 8 89.9; v. slight haze 80.9;v. hazy 81.1; v. hazy 4 10 91.7; v. slight haze 76.5; cloudy 76.3;cloudy 5 15 92.8; v. slight haze 77.2; v. hazy 76.9; cloudy 6 20 87.5;slight haze 71.2; cloudy 70.4; cloudy 7 30 91.0; v. slight haze 76.6;cloudy 75.5; cloudy

After taking the transmittance readings, the beakers were allowed tocool down. The solutions were then poured out and the beakers wererinsed with deionized water. All of the beakers had precipitation on thebottom.

The beakers were then set upside-down to dry to check for adheringprecipitation on the beakers. The next day, a few drops of dilute HClwere put into the beakers. All of the solutions except for the 8 ppmsolution (Sample 3) had visible carbonate residue and slight bubblingwith the addition of the HCl, indicating the presence of carbonate.

As can be seen in Table 2, the transmittance readings were highest whenthe concentration of the acrylate-maleic copolymer was between about 5ppm and 30 ppm, and particularly at about 5 ppm and 8 ppm. Although thesolutions had relatively high transmittance readings at 10 ppm, 20 ppmand 30 ppm, the solutions turned cloudy between 85° F. and 140° F.Similarly the solution including about 15 ppm of acrylate-maleiccopolymer turned cloudy between 140° F. and 160° F.

Samples 8, 9, 10, 11, 12, 13 and 14

Samples 8, 9, 10, 11, 12, 13 and 14 included varying concentrations ofan acrylate polymer having a molecular weight of about 4,500 g/mol(Acusol 445N), an acrylate-maleic copolymer having a molecular weight ofabout 40,000 g/mol (Acusol 505N) and a phosphonocarboxylic acid(Bayhibit AM). In particular, the samples were prepared by mixing 97.14grams of deionized water and 2.86 grams of Acusol 505N, mixing 97.78grams of deionized water and 2.22 grams of Acusol 445N and mixing 98.0grams of deionized water and 2.0 grams of Bayhibit AM.

Because the results of Samples 1-7 illustrated that solutions includingeither 5 ppm or 8 ppm acrylate-maleic copolymer produced the highesttransmittance levels, Samples 8-14 included either 5 ppm or 8 ppmacrylate-maleic copolymer. The amount of acrylate polymer was alsovaried. The amount of phosphonocarboxylic acid remained constant at 8ppm.

Table 3 shows the component concentrations and transmittance readings at85° F., 140° F. and 160° F. of each of Samples 8-14. The appearances ofthe solutions were also noted.

TABLE 3 Concentrations Transmittance Reading (%) Sample Component (ppm)85° F. 140° F. 160° F. 8 Acusol 505N 5 98.2; clear 94.1; 91.5; BayhibitAM 8 slight slight Acusol 445N — haze haze 9 Acusol 505N 5 98.3; clear96.0; v. 90.8; Bayhibit AM 8 slight slight Acusol 445N 10 haze haze 10Acusol 505N 8 96.6; v. 92.5; 89.7; hazy Bayhibit AM 8 slight slightAcusol 445N 10 haze haze 11 Acusol 505N 5 96.4; v. 95.0; 91.5; BayhibitAM 8 slight slight slight Acusol 445N 20 haze haze haze 12 Acusol 505N 897.9; v. 95.2; 90.4; hazy Bayhibit AM 8 slight slight Acusol 445N 20haze haze 13 Acusol 505N 5 97.2; v. 96.1; v. 90.1; hazy Bayhibit AM 8slight slight Acusol 445N 30 haze haze 14 Acusol 505N 8 97.3; v. 95.9;89.9; hazy Bayhibit AM 8 slight slight Acusol 445N 30 haze haze

After taking the transmittance readings and allowing the beakers to cooldown, all of the solutions were poured out and the beakers were rinsedwith deionized water. All of the beakers had precipitation at the bottomof the beakers.

The beakers were then set upside-down to dry to check for precipitationon the beakers. The next day, a few drops of dilute HCl were put intothe beakers. All of the solutions had visible carbonate residue andslight bubbling with the addition of the HCl, indicating the presence ofcarbonate.

As illustrated in Table 3, all of the Samples had transmittance readingsof 89. % or higher. In particular, Samples 9, 11, 12, 13 and 14 producedtransmittance readings of at least 96%, 95%, and 90% at 85° F., 140° F.and 160° F., respectively.

Samples 15, 16, 17, 18 and 19

After determining from Samples 8-14 that compositions including betweenabout 5 ppm and about 8 ppm of acrylate-maleic copolymer and higherlevels of acrylate polymer yielded high transmittance rates, a pluralityof compositions were formed with varying amounts of acrylate-maleiccopolymer and phosphonocarboxylic acid and generally higherconcentrations of acrylate polymer.

Samples 15, 16, 17, 18 and 19 included varying concentrations of anacrylate polymer having a molecular weight of about 4,500 g/mol (Acusol445N), an acrylate-maleic copolymer having a molecular weight of about40,000 g/mol (Acusol 505N) and a phosphonocarboxylic acid (Bayhibit AM).In particular, the samples were prepared by first mixing 97.14 grams ofdeionized water and 2.86 grams of Acusol 505N, mixing 97.78 grams ofdeionized water and 2.22 grams of Acusol 445N and mixing 98.0 grams ofdeionized water and 2.0 grams of Bayhibit AM.

Table 4 shows the component concentration and transmittance readings at85° F., 140° F. and 160° F. for each of Samples 15-19. The appearancesof the solutions were also noted.

TABLE 4 Concentrations Transmittance Reading (%) Sample Component (ppm)85° F. 140° F. 160° F. 15 Acusol 505N 5 99.3; clear 97.3; v. 96.1;Bayhibit AM 8 slight slight Acusol 445N 40 haze haze 16 Acusol 505N 598.6; clear 96.9; v. 93.5; Bayhibit AM 6 slight slight Acusol 445N 40haze haze 17 Acusol 505N 5 96.9; v. 95.6; 89.6; hazy Bayhibit AM 6slight slight Acusol 445N 30 haze haze 18 Acusol 505N 7 99.0; clear97.7; v. 95.3; Bayhibit AM 8 slight slight Acusol 445N 40 haze haze 19Acusol 505N 8 99.4; clear 98.3; v. 96.1; Bayhibit AM 8 slight slightAcusol 445N 40 haze haze

After taking the transmittance readings and allowing the beakers to cooldown, all of the solutions were poured out and the beakers were rinsedwith deionized water. All of the beakers had precipitation at the bottomof the beakers, although the precipitation of the beakers that contained8 ppm Bayhibit (Samples 15, 18 and 19) was lighter.

The beakers were then set upside-down to dry to check for precipitationon the beakers. The next day, a few drops of dilute HCl were put intothe beakers. All of the solutions had visible carbonate residue andslight bubbling with the addition of the HCl, indicating the presence ofcarbonate. Sample 19 had almost no residual or fizzing.

As can be seen in Table 4, again all of the samples resulted intransmittance readings of at least 89.5%. However, Samples 15 and 19produced the highest transmittance readings, yielding transmittancereadings of at least 99%, 97% and 95% at 85° F., 140° F. and 160° F.,respectively. Overall, Sample 15, which included 40 ppm acrylatepolymer, 8 ppm phosphonocarboxylic acid and 5 ppm acrylate-maleiccopolymer, yielded the highest transmittance levels.

Samples 20 and 21

Based on the results of Samples 15-19, Samples 20 and 21 wereformulated, varying only the amount of phosphonocarboxylic acid.

Samples 20 and 21 included varying concentrations of an acrylate polymerhaving a molecular weight of about 4,500 g/mol (Acusol 445N), anacrylate-maleic copolymer having a molecular weight of about 40,000g/mol (Acusol 505N) and a phosphonocarboxylic acid (Bayhibit AM). Inparticular, the samples were prepared by first mixing 97.14 grams ofdeionized water and 2.86 grams of Acusol 505N, mixing 97.78 grams ofdeionized water and 2.22 grams of Acusol 445N and mixing 98.0 grams ofdeionized water and 2.0 grams of Bayhibit AM.

Table 5 shows the component concentration and transmittance readings at85° F., 140° F. and 160° F. of each of Samples 20 and 21. The appearanceof each of the solutions was also noted.

TABLE 5 Concentrations Transmittance Reading (%) Component (ppm) 85° F.140° F. 160° F. Sample 20 Acusol 505N 5 99.5; clear 97.0; v. 96.2;Bayhibit AM 10 slight slight Acusol 445N 40 haze haze Sample 21 Acusol505N 5 99.7; clear 97.3; v. 94.8; Bayhibit AM 12 slight slight Acusol445N 40 haze haze

After taking the transmittance readings and allowing the beakers to cooldown, all of the solutions were poured out and the beakers were rinsedwith deionized water. All of the beakers had precipitation at the bottomof the beakers.

The beakers were then set upside-down to dry to check for precipitationon the beakers. The next day, a few drops of dilute HCl were put intothe beakers.

A glass vial containing Samples 20 and 21 were then put in ovens heatedto about 160° F. for about 2 hours and 40 minutes to simulate theconditions of a washing machine. After removing the vials from the oven,the vials did not have residue sticking to the sides.

The results in Table 5 show that compositions including either 10 ppm or12 ppm phosphonocarboxylic acid yield high transmittance readings.Although Sample 21 produced slightly higher transmittance readings atthe low and intermediate temperature, Sample 20 had a slightly highertransmittance reading at 160° F. However, the differences between thetransmittance readings of the two samples did not exceed 2% at any ofthe temperatures. When the results from Samples 20 and 21 were comparedto the results for Sample 15 (Table 4), it is clear that an increase inthe phosphonocarboxylic acid concentration did not improve the results.

100 Cycle Warewash Test

A 100 cycle warewash test was performed using six 10 oz. Libbey glassesand one plastic tumbler to determine the film accumulation on theglasses and plastic tumbler after washing in an institutional warewashmachine. The tests were performed on a Hobart AM-14 warewash machineusing either 10 or 17 grain water (1 grain=17 ppm). The washbath volumewas 60 L, the rinse volume was 4.5 L, the wash time was 40 seconds andthe rinse time was 9 seconds with a 4 second dwell time between the washand rinse cycle.

6 Libbey glasses were prepared by removing all film and foreign materialfrom the surfaces of the glasses. The plastic tumbler was new and thusdid not need to be cleaned prior to testing. The dishmachine was thenfilled with an appropriate amount of water and the water was tested forhardness. After recording the water hardness value, the tank heaterswere turned on. The dishmachine was then turned on and wash/rinse cycleswere run through the machine until a wash temperature of between about150° F. and about 160° F. and a rinse temperature of between about 175°F. and about 190° F. were reached. The controller was then set todispense an appropriate amount of detergent into the wash tank. Thesolution in the wash tank was titrated to verify detergentconcentration.

The 6 clean glasses were placed diagonally in a Raburn rack and oneplastic tumbler was placed off-diagonally in the Raburn rack (see FIGUREbelow for arrangement) and the rack was placed inside the dishmachine.(P=plastic tumbler; G=glass tumbler).

The 100 cycle test was then started. At the beginning of each washcycle, the appropriate amount of detergent was automatically dispensedinto the warewash machine to maintain the initial detergentconcentration. The detergent concentration was controlled byconductivity.

At the completion of each cycle, the proper amount of detergent wasdispensed into the warewash machine to maintain the initialconcentration. Upon completion of 100 cycles, the rack was removed fromthe warewash machine and the glasses and plastic tumbler were allowed todry overnight.

The glasses and plastic tumbler were then graded for film accumulationusing a strong light source. This method is used to estimate the amountof spots and films on the glasses and plastic tumblers using a scale of1 to 5. A rating of 1 indicated no films. A rating of 2 indicated atrace amount of film that was barely perceptible under intense spotlight conditions. A rating of 3 indicated a light film was present whenheld up to a florescent light source. A rating of 4 indicated that amedium amount of film was present such that the surface appeared hazywhen held up to a florescent light source. A rating of 5 indicated thata heavy amount of filming was present such that the surface appearscloudy when held up to a florescent light source.

The ratings of the glasses were averaged to determine an average glassrating. Generally, a composition is considered effective if the testedglasses and plastic tumbler receive a visual rating of about 3.5 or lessusing 17 GPG water and about 2.5 or less using 10 GPG water.

Lightbox Test

The glasses were also evaluated using a lightbox. The lightbox teststandardizes the evaluation of the glasses and plastic tumbler run inthe 100 cycle test using an analytical method. The lightbox test isbased on the use of an optical system including a photographic camera, alightbox, a light source and a light meter. The system is controlled bya computer program (Spot Advance and Image Pro Plus).

To evaluate the glasses, each glass was placed on the lightbox restingon its side and the intensity of the light source was adjusted to apredetermined value using a light meter. The conditions of the 100 cycletest were entered into the computer. A picture of the glass was takenwith the camera and saved on the computer for analysis by the program.The picture was analyzed using the upper half of the glass in order toavoid the gradient of darkness on the film from the top of the glass tothe bottom of the glass, based on the shape of the glass.

Generally, a lower lightbox rating indicates that more light was able topass through the glass. Thus, the lower the lightbox rating, the moreeffective the composition was at preventing scaling on the surface ofthe glass. A composition is considered effective if the tested glassreceived a lightbox rating of about 40,000 or less using 17 GPG waterand about 25,000 or less using 10 GPG water.

Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 and Comparative Example A

Examples 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 are compositions of thepresent invention, with component concentrations (in weight percent) ofsodium hydroxide (liquid and solid forms), water, an acrylate polymer(Acusol 445N, 445ND or Sokalan PA40), an acrylate-maleic copolymer(Acusol 505N, Acusol 448 or Sokalan CP5), a phosphonocarboxylic acid(Bayhibit AM), a surfactant (Pluronic N3), sodium sulfate and sodiumcarbonate (soda ash or dense ash), as provided in Table 6. Duringprocessing, the mixture was kept at a temperature of between about 160°F. and about 170° F. The product was then chilled in a freezer for aminimum of about 1 hour.

The composition of Comparative Example A included a known cleaningcomposition, Solid Power, available from Ecolab Inc., St. Paul, Minn.

The water used in testing the compositions of Examples 1, 2, 3, 4, 5, 6,7, 8, 9 and 10 and Comparative Example A was 17 grains per gallon (GPG)water. Using 17 GPG water allowed for observation of differences afteronly 100 cycles or less.

Table 6 provides the component concentrations for the compositions ofExamples 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10.

TABLE 6 Concentration (wt %) Component Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex.6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Acusol 505N 1.430 1.430 1.430 1.430 1.4301.430 0.000 0.000 0.000 0.000 (35%) Acusol 448 0.000 0.000 0.000 0.0000.000 0.000 1.090 0.000 1.090 0.000 Sokalan CP5 0.000 0.000 0.000 0.0000.000 0.000 0.000 1.250 0.000 1.250 Acusol 445N 0.000 0.000 8.900 8.9008.900 0.000 0.000 0.000 8.900 8.900 (45%) Acusol 445ND 4.500 4.500 0.0000.000 0.000 0.000 0.000 0.000 0.000 0.000 Sokalan PA40 0.000 0.000 0.0000.000 0.000 11.4 11.400 11.400 0.000 0.000 Bayhibit AM 1.600 3.200 3.2006.400 1.600 1.600 1.600 1.600 1.600 1.600 Sodium 10.000 10.000 10.0008.000 10.000 9.000 9.000 8.000 8.000 9.000 Hydroxide, liquid (50%)Sodium 28.000 28.000 28.000 29.000 28.000 28.000 28.000 28.000 29.00028.000 Hydroxide, beads Water 4.500 4.500 0.000 0.000 1.500 4.000 4.0000.000 0.000 0.000 Sodium Chlorite 0.250 0.250 0.250 0.250 0.250 0.2500.250 0.250 0.250 0.250 Solution (25%) Pluronic N3 1.200 1.200 1.2001.200 1.200 1.200 1.200 1.200 1.200 1.200 Sodium Sulfate, 14.000 14.00014.000 14.000 14.120 13.120 13.500 14.300 17.000 16.800 anhydrous Sodium34.520 32.920 33.020 30.820 33.000 33.000 33.000 33.000 33.000 33.000Carbonate

Table 7 provides the visual ratings and lightbox ratings for each of thecompositions of Examples 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 andComparative Example A at 1000 ppm detergent concentration in 17 GPGwater.

TABLE 7 Visual Rating (Glass/Plastic) Lightbox Rating Ex. 1  3.88/1.7535273.41 Ex. 2 3.83/2   29683.75 Ex. 3 3.88/2   32237.35 Ex. 4 4.17/2  33575.40 Ex. 5 3.64/2.5 30405.28 Ex. 6 2.42/1   32707.67 Ex. 7 3.00/1  35820.00 Ex. 8 3.17/1.5 40948.17 Ex. 9 3.33/1.5 38531.50 Ex. 10 3.17/1.539906.00 Comp. Ex. A 3.93/2.5 28854.29

As can be seen in Table 7, when the glasses and plastic tumbler weretested using 17 GPG water, all of the compositions resulted in similarvisual ratings as the composition of Comparative Example A. The onlyexception was the composition of Example 6, which resulted in acceptablevisual ratings for both the glasses and plastic tumbler. Thecompositions of Examples 6 and 7 resulted in the lowest overall visualscores for both the glasses and plastic tumblers.

Similarly, the compositions of Examples 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10and Comparative Example A produced acceptable lightbox ratings using 17GPG water. The composition of Comparative Example A yielded the lowestlightbox rating. The lightbox ratings of the glasses treated with thecompositions of Examples 2 and 5 were most similar to the lightboxratings of the glasses treated with the composition of ComparativeExample A, differing by only about 2.87% and about 5.38%, respectively.

Examples 2, 5, 6 and 9 and Comparative Example A

After visually inspecting the glasses and plastic tumbler treated withthe compositions of Examples 1-10 using 17 GPG water, the compositionsof Examples 2, 5, 6 and 9 were tested again. However, rather than using17 GPG water, 10 GPG water was used. Using 10 GPG water provides anaverage level of water hardness generally found in the United States.

The composition of Comparative Example A included a known cleaningcomposition, Solid Power, available from Ecolab Inc., St. Paul, Minn.

Table 8 provides the visual ratings and lightbox ratings for each of thecompositions of Examples 2, 5, 6 and 9 and Comparative Example A.

TABLE 8 Example Example Example Example Comp. 2 5 6 9 Example A Visual2.5/1 2/2 1/1.5 1/1 2.21/3.5 Rating (Glass/ Plastic) Lightbox 22330.6718755.69 18659 15334.5 19082.84 Rating

As can be seen in Table 8, both the glasses and plastic tumbler treatedwith the compositions of Examples 2, 5, 6 and 9 had acceptable visualratings of 2.5 or less when tested using 10 GPG water. By contrast,while glasses treated with the composition of Comparative Example Aresulted in an acceptable visual rating, the plastic tumbler treatedwith the composition of Comparative Example A did not result in anacceptable visual rating.

The compositions of Examples 5, 6 and 9 yielded lightbox ratings similarto or lower than the composition of Comparative Example A with ratingsbelow 25,000. All of the compositions of Examples 2, 5, 6 and 9 andComparative Example A had acceptable lightbox ratings. In particular,the lightbox ratings of the glasses treated with the compositions ofExamples 5, 6 and 9 had lower lightbox ratings than glass treated withthe composition of Comparative Examples A by about 1.7%, 2.22% and19.64%, respectively.

Various modifications and additions can be made to the exemplaryembodiments discussed without departing from the scope of the presentinvention. For example, while the embodiments described above refer toparticular features, the scope of this invention also includesembodiments having different combinations of features and embodimentsthat do not include all of the above described features.

The following is claimed:
 1. A water hardness controlling agentconsisting essentially of: (a) a polyacrylic acid or salt thereof havinga molecular weight of between about 1,000 and about 50,000 g/mol; (b) anacrylic-maleic acid copolymer or salt thereof having a molecular weightof between about 1,000 and about 100,000 g/mol; and (c) aphosphonocarboxylic acid or salt thereof, wherein a ratio ofacrylic-maleic acid copolymer or salt thereof to polyacrylic acid orsalt thereof to phosphonocarboxylic acid or salt thereof in parts permillion is about 1-30:10-80:6-20.
 2. The water hardness controllingagent of claim 1, wherein the ratio of acrylic-maleic acid copolymer orsalt thereof to polyacrylic acid or salt thereof to phosphonocarboxylicacid or salt thereof in parts per million is about 5:40:8.
 3. The waterhardness controlling agent of claim 1, wherein the polyacrylic acid orsalt thereof has a molecular weight of between about 1,000 and about35,000 g/mol.
 4. The water hardness controlling agent of claim 1,wherein the acrylic-maleic acid copolymer or salt thereof has amolecular weight of between about 1,000 and about 75,000 g/mol.
 5. Thewater hardness controlling agent of claim 1, wherein the polyacrylicacid or salt thereof has a molecular weight of about 4,500 g/mol and theacrylic-maleic acid copolymer or salt thereof has a molecular weight ofabout 40,000 g/mol.
 6. The water hardness controlling agent of claim 1,wherein the phosphonocarboxylic acid or salt thereof comprises2-phosphonobutane 1, 2, 4 tricarboxylic acid.